21. 23. 9.

2011, Brno, Czech Republic, EU

DRAWING- THE PRODUCTION OF INDIVIDUAL NANOFIBERS BY EXPERIMENTAL
METHOD
Jana BAJKOV
a
, Ji CHALOUPEK
a
, David LUK
a
, Maxime LACARIN

a
Technical University of Liberec, Faculty of Textile Engineering, Department of Nonwovens,
Studentsk 2, 461 17 Liberec, Czech Republic, JanaBajakova@seznam.cz
Abstract
This paper describes the production technology of individual nanofibers by "drawing". It is a relatively new
method and the first mention of it is in the professional publication from 1998
1
.
By method of electrospinning we can produce layer of nanofibers. In this layer, however, individual
nanofibers can not be separated without their destruction. Electrospinning does not produce single
nanofibers, in contrast to the method of "drawing". It is based on the principle of drawing nanofibers from
polymer droplet at a specific rate, depending on the type of polymer. The biggest advantage of this method is
the possibility of study the properties of individual nanofibers and its minimal demands on the device.
Intended use of single nanofibers is in nano-optics, nano-electronics, tissue engineering and production of
yarns with a precisely defined number of nanofibers. The aim of this paper is approximations of production
these individual nanofibers and their subsequent analysis.
Keywords: drawing, polymer nanofibers, micropipette, yarn from nanofibers
1. INTRODUCTION
Production of polymer fibers with diameters ranging from micron to nanometer scales has generated
significant interest due to its potential impact in many applications such as nano-electronics and optical
sensors. These applications require the fabrication of one (1D), two (2D) and three-dimensional (3D) network
of nanofibers. At first, the individual components are created and assembled together into larger structures.
The first step in such a manufacturing approach involves fabricating fibers. Of all techniques, electrospinning
is the most popular process that allows for the continuous production of fibers ranging from tens of
nanometer to a few microns in diameter. By method of electrospinning we can produce layer of nanofibers.
In this layer, however, individual nanofibers can not be separated without their damage. Electrospinning
does not produce single nanofibers, in contrast to the method of "drawing. [2]
On the other hand, in the drawing process, the fibers are fabricated by contacting a previously deposited
polymer solution droplet with a sharp tip and drawing it as a liquid fiber which is then solidified by rapid
evaporation of the solvent due to the high surface area. The drawn fiber can be connected to another
previously deposited polymer solution droplet thus forming a suspended fiber. Here, the predeposition of
droplets significantly limits the ability to extend this technique, especially in free dimensional configurations
and hard to access spatial geometries. Furthermore, there is a specific time in which the fibers can be pulled.
Viscosity of the droplet continuously increases with time due to solvent evaporation from the deposited
droplet. The continual shrinkage in the volume of the polymer solution droplet affects the diameter of the
fiber drawn and limits the continuous drawing of fibers. [2]
To overcome the above-mentioned limitation is appropriate to use hollow glass micropipettes with a
continuous polymer dosage. It provides greater flexibility in drawing continuous fibers in any configuration.
Moreover, this method offers increased flexibility in the control of key parameters of drawing such as waiting
time before drawing (due to the required viscosity of the polymer edge drops), the drawing speed or
viscosity, thus enabling repeatability and control on the dimensions of the fabricated fibers. [2]

21. 23. 9. 2011, Brno, Czech Republic, EU


2. TECHNOLOGY
There are several ways to make single nanofibers. The simplest of these is schematically illustrated in Fig. 1.
On the substrate material is applied a millimeter drop of polymer solution (A). Micropipette then moves down
toward the edge of the drop (B), there is contact and by back motion of micropipette the fiber is to pull out of
polymer droplet at a certain rate, depending on the type of polymer (C).The liquid polymer is formed in the
fiber. The resultant cross section depends very much on the exact material composition, drawing velocity
and speed evaporation of solvent.

Fig. 1 Illustration of the basic production process of nanofibers by drawing from droplet of the polymer [1].
This procedure for the production of nanofibers is implemented through micropipettes. However, there is the
possibility of producing nanofibers using an instrument called a micromanipulator. It is specially designed for
this method and is currently working on its construction and subsequent use in practice. Micromanipulator
provides a continuous supply of the exact amount of polymer to the probe, which is connected to the
positioner. The probe is lowered onto the substrate, the polymer flows and there is a drawing of polymer fiber
at a given distance with a precisely defined extension speed.
3. EXPERIMENT
Although the above process for the production nanofibers (Fig. 1) is very easy, here plays an important role
mainly material from which fiber is produced. Fiber drawing requires a viscoelastic material that can hold on
a strong deformations and tensions during pulling. Albeit not all materials are suitable for produce of
individual nanofibers by this method, we managed to produce nanofibers from the following materials
(Tab.1):
Table 1 Type of materials and diameters of individual nanofibers obtained from them by drawing process.
Type of materials
Diameter of nanofibers variation [nm]
Polycaprolacton (PCL) 27030
Polyvinylalcohol (PVA) 20040
Blend of Hyaluronic acid (HA) and Fish gelatin (FG) 47070
Polyethylene oxide (PEO) 53060
Polyvinyl butyral (PVB) 60090
Polymethylmethacrylate (PMMA) 56040
From all of these materials above we can produce fibers with diameters smaller than a micron. In Fig. 2 is an
image of nanofiber from optical microscopy from polymer PCL with a diameter of 270 nm. PCL is a suitable
material for tissue engineering. In Fig. 3 is a picture of PVA nanofiber with a diameter of 200 nm (Mw=67 000
g/mol, c=40%). It is the finest fiber that we managed to obtain by this method. In Fig. 4 is a PMMA fiber with
a diameter of 560 nm. Possible application of PMMA nanofibers is in nano-optics due to light conductivity of
this material. In Fig. 5 is a fiber pulled from a blend of Hyaluronic acid and Fish gelatin with a diameter of 900
nm. The fibers are usually pulled on a paper substrate; the structure of the paper is also seen in the images.
21. 23. 9. 2011, Brno, Czech Republic, EU


Fig. 2 PCL nanofiber (270nm) Fig. 3 PVA nanofiber (200nm)
Fig. 4 PMMA nanofiber (560nm) Fig. 5 Fiber from a bland HA+FG (900nm)

The process was always the same, only with regard to the specific properties of the polymer. It was always
necessary to prepare a concentration series of polymer solution for subsequent testing and finding the best
solution viscosity. Concentration and molecular weight of polymer have a significant impact on the actual
pulling with a micropipette and the final fiber diameter. But we cant definitely say about what the
dependence is. This can be seen in Fig. 6 below. There are shown the finest PVA fiber diameters depending
on the concentration and molecular weight of polymer used. Dependence for all three molecular weights is
fluctuating. The finest fibers were pulled from 20% PVA solutions, as you can see in Tab. 2. Extension rate
for all materials was 0,03 m/sec.
21. 23. 9. 2011, Brno, Czech Republic, EU


Fig. 6 Diameter of PVA nanofibers depending on the molecular weight and concentration of polymer solution
Table 2 Diameter of PVA nanofibers, molecular weight and concentration of polymer solution
Concentration c[%] Molecular weight M
w
[g/mol] Diameter of nanofiber variation d[nm]
20
61 000 26030
125 000 27020
130 000 50050
30
61 000 46040
125 000 93020
130 000 30040
40
61 000 37090
125 000 41090
130 000 60040
As you can see in Tab. 2, we managed to produce nanofibers by drawing from all tested polymer solutions of
PVA. Not all of them, however, work simply.
We assumed the subsequent use of nanofibers in practice, for example for the production of yarn. Therefore,
our effort was to find a solution of PVA polymer with which the work will be easily and it will be able to
repeatedly produce nanofibers at least 10 cm long. That we managed by repeated tests with just 40% PVA
(Mw 67 000 g/mol). The image of our first yarn from the electron microscope is shown in Fig. 7. Yarn was
made by hand from several hundred fibers with diameters ranging from 200 to 3500nm. In Fig. 8 you can
see the frequency of fibers diameters in the yarn. The most contained fibers in the yarn have diameters from
400 to 600nm (37%), followed by fibers from 200 to 400nm (22%). Approximately 75% contained fibers have
a diameter below the micron.





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Fig. 7 PVA yarn from nanofibers Fig. 8 Frequency of fibers diameters in the yarn
4. CONCLUSIONS
Our aim was to produce single nanofibers by pulling from the polymer droplets using a micropipette, as
shown in the paper, Fig. 1. We succeeded for several polymer materials, namely PVA, PCL, PVB, PEO and
PMMA. The finest fiber that we managed to obtain is from PVA with a diameter of 200nm (Mw=67 000g/mol).
The advantage of this method is possibility of precise puting of pulled nanofibers from which we can produce
complicated network (parallel or intersecting fibers). We also took advantage of this and produced the yarn
from parallel arranged PVA fibers, as shown in Fig. 7. The yarn is consists of several hundred fibers and
contains both nanofibers and also fibers with a diameter of micron. It is not desired, so we will focus on the
production of yarns from only a few pulled fibers in the future. It will be much easier to analyze and the
resulting yarn will be consist of exactly defined number of nanofibers.
ACKNOWLEDGEMENT
The authors are thankful to Research grant GAR 102/08/H081 and TO Ministry of Education,
Youth and Sports of the Czech Republic (STUDENTS GRANT COMPETITION TUL IN SPECIFIC
UNIVERSITY RESEARCH IN 2011 - PROJECT NO. 4843) for their financial support.
LITERATURE
[1] Ondaruhu T., Joachim C.: Drawing a single nanofibre over hundreds of microns. Europhysics letters, 42 (2), pp.
215-220, (1998)
[2] Amrinder S. Nain, Joanna C.Wong, Cristina Amon, Metin Sitti: Drawing suspended polymer micro/nanofibers
using glass micropipettes. Applied Physics Letters, 89 (18), pp. 183105-7, (2006)
[3] Xiaobo Xing, Yuqing Wang, and Baojun Li: Nanofiber drawing and nanodevice assembly in poly (trimethylene
terephthalate). Optics express, 16 (14), (2008)
[4] Ramakrishna S., Kazutoshi F., Wee-Eong T., Teik-Cheng L., Zuwei M.: Electrospinning and Nanofibers, pp. 7-13,
(2005)